CN110874013A - Photosensitive resin composition, photosensitive resin layer using same, and color filter - Google Patents
Photosensitive resin composition, photosensitive resin layer using same, and color filter Download PDFInfo
- Publication number
- CN110874013A CN110874013A CN201910400724.8A CN201910400724A CN110874013A CN 110874013 A CN110874013 A CN 110874013A CN 201910400724 A CN201910400724 A CN 201910400724A CN 110874013 A CN110874013 A CN 110874013A
- Authority
- CN
- China
- Prior art keywords
- photosensitive resin
- resin composition
- substituted
- unsubstituted
- chemical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention discloses a photosensitive resin composition, a photosensitive resin layer manufactured by using the photosensitive resin composition and a color filter, wherein the photosensitive resin composition comprises: a colorant comprising (a) (a-1) a blue pigment, a blue dye, or a mixture thereof; (a-2) a yellow dye having a maximum absorption wavelength in a wavelength region of 360 nm to 390 nm and a transmittance of 95% or more in a wavelength region of 450 nm to 900 nm; and (a-3) a violet dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority and benefit from korean patent application No. 10-2018-0103735 filed by the korean intellectual property office at 31/8/2018, the entire contents of which are incorporated herein by reference.
Technical Field
The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the photosensitive resin composition, and a color filter.
Background
Among many types of displays, the liquid crystal display device has advantages in brightness, thinness, low cost, low operation power consumption, and improved adhesion to integrated circuits, and has been more widely used for notebook computers, monitors, and TV screens. The liquid crystal display device includes a lower substrate on which a black matrix (light blocking layer), a color filter, and an ITO pixel electrode are formed, and an upper substrate on which an activation circuit part including a liquid crystal layer, a thin film transistor, and a capacitor layer are formed.
The color filter is formed in the pixel region by sequentially stacking a plurality of color filters (generally, formed of three primary colors, such as red (R), green (G), and blue (B)) in a predetermined order to form each pixel, and a black matrix (light blocking layer) is disposed on a transparent substrate in a predetermined pattern to form a boundary between the pixels.
The pigment dispersion method, which is a method of forming a color filter, provides a color thin film by repeating a series of processes, such as coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix, exposing the formed pattern to light, removing an unexposed portion with a solvent, and thermally curing it. A colored photosensitive resin composition for manufacturing a color filter according to the pigment dispersion method generally contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, and the like. The pigment dispersion method is actively used to manufacture LCDs such as mobile phones, notebook computers, monitors, and TVs.
However, the photosensitive resin composition of a color filter using a pigment dispersion method having many advantages has some disadvantages because there are difficulties in finely pulverizing the powder, various additives are required for stabilizing (even dispersing) the dispersion liquid and a complicated process, and further, the optimum quality of the pigment dispersion liquid is maintained under complicated storage and transportation conditions.
In addition, a color filter manufactured using the pigment-type photosensitive resin composition is limited in brightness and contrast ratio due to the pigment particle size. A color image sensor device for an image sensor requires a small dispersion particle diameter to form a fine pattern. In response to this demand, attempts have been made to prepare photosensitive resin compositions by introducing dyes instead of or together with pigments to realize color filters having improved color characteristics such as brightness, contrast ratio and the like, but the dye-type photosensitive resin compositions have a problem of deterioration in durability as compared with pigment-type photosensitive resin compositions.
Disclosure of Invention
An embodiment provides a photosensitive resin composition having excellent brightness when it is capable of realizing high color coordinates by minimizing the amount of a colorant.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Another embodiment provides a color filter including the photosensitive resin layer.
An embodiment of the present invention provides a photosensitive resin composition, including: a colorant comprising (a) (a-1) a blue pigment, a blue dye, or a mixture thereof; (a-2) a yellow dye having a maximum absorption wavelength in a wavelength region of 360 nm to 390 nm and a transmittance of 95% or more in a wavelength region of 450 nm to 900 nm; and (a-3) a violet dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.
The violet dye may be included in an amount of 0.1 to 2% by weight based on the total amount of the photosensitive resin composition.
The violet dye may be represented by chemical formula 1-1 or chemical formula 1-2.
[ chemical formula 1-1]
[ chemical formulas 1-2]
In chemical formula 1-1 and chemical formula 1-2,
R101to R105Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R106is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,
R107is a substituted or unsubstituted C3 to C20 cycloaliphatic ring group or a substituted or unsubstituted C6 to C20 aryl group,
R108to R110Independently a substituted or unsubstituted C1 to C20 alkyl group,
n is an integer in the range of 1 to 5, and
l is represented by chemical formula 1-3,
[ chemical formulas 1-3]
*-L1-A
Wherein, in chemical formulas 1 to 3,
L1is-O (C ═ O) -,
a is a substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 alicyclic ring group, or substituted or unsubstituted C6 to C20 aryl group.
In chemical formula 1-2, L may be represented by one of chemical formulas 1-3-1 to 1-3-5.
[ chemical formula 1-3-1]
[ chemical formulas 1-3-2]
[ chemical formulas 1-3-3]
[ chemical formulas 1-3-4]
[ chemical formulas 1-3-5]
In chemical formulas 1-3-1 to 1-3-5,
R111is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group,
R112to R114Independently is hydroxy or substituted or unsubstituted C1 to C10 alkyl with the proviso that R is112And R113At least one of which is a hydroxyl group,
R115is a substituted or unsubstituted C1 to C10 alkyl group，
o and p are independently integers in the range of 1 to 3 with the proviso that 2. ltoreq. o + p. ltoreq.5, and
q is an integer in the range of 0 to 4.
In the violet dye represented by chemical formula 1-2, R106May be a hydrogen atom, R107May be substituted or unsubstituted adamantyl, R108To R110May be independently a substituted or unsubstituted C1 to C20 alkyl group, and L may be represented by chemical formula 1-3-1.
The yellow dye may be an azo-type dye.
The yellow dye may be included in an amount of 0.01 wt% to 1 wt% based on the total amount of the photosensitive resin composition.
The yellow dye may be included in a smaller amount than the violet dye, and the violet dye is included in a smaller amount than the blue colorant.
The binder resin may include acryl-based binder resin, cardo-based binder resin (cardo-based binder resin), or a combination thereof.
The photosensitive resin composition may comprise, based on the total amount of the photosensitive resin composition: 2 to 40 weight percent of a colorant; 3 to 20% by weight of a binder resin; 1 to 10% by weight of a photopolymerizable compound; 0.1 to 5% by weight of a photopolymerization initiator; and the balance solvent.
The photosensitive resin composition may further include an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.
When the By value is 0.0510 in the CIE color coordinates, the photosensitive resin composition can have the Bx value less than or equal to 0.148.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Another embodiment provides a color filter including the photosensitive resin layer.
Other embodiments of the invention are encompassed by the following detailed description.
The photosensitive resin composition according to the embodiment can minimize the amount of the blue pigment to achieve a lower Bx color coordinate in a high color blue resist and prevent a decrease in brightness.
Detailed Description
Embodiments of the present invention are described in detail below. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of the claims.
In the present specification, when a specific definition is not otherwise provided, "substituted" means substituted by a substituent selected from: halogen (F, Br, Cl or I), hydroxy, nitro, cyano, amino (NH)2、NH(R200) Or N (R)201)(R202) Wherein R is200、R201And R202Identical or different and independently C1 to C10 alkyl), carbamimidoyl, hydrazino, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group, and substituted or unsubstituted heterocyclic group.
In the present specification, when a specific definition is not otherwise provided, "alkyl" means a C1 to C20 alkyl group, and specifically a C1 to C15 alkyl group, "cycloalkyl" means a C3 to C20 cycloalkyl group, and specifically a C3 to C18 cycloalkyl group, "alkoxy" means a C1 to C20 alkoxy group, and specifically a C1 to C18 alkoxy group, "aryl" means a C6 to C20 aryl group, and specifically a C6 to C18 aryl group, "alkenyl" means a C2 to C20 alkenyl group, and specifically a C2 to C18 alkenyl group, "alkylene" means a C1 to C20 alkylene group, and specifically a C1 to C18 alkylene group, and "arylene" means a C6 to C20 arylene group, and specifically a C6 to C16 arylene group.
In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate", and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid", when a specific definition is not otherwise provided.
In the present specification, the term "combination" means mixing or copolymerization when a definition is not otherwise provided. Further, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymer to random copolymer.
In the chemical formulae of the present specification, unless a specific definition is provided otherwise, when a chemical bond is not drawn at a position that should be given, the hydrogen bonds at the position.
In the present specification, the CIE color coordinates refer to CIE1931 color coordinates.
In the present specification, the pyridoxine-containing resin refers to a resin comprising at least one functional group selected from chemical formula 10-1 to chemical formula 10-11.
In the present specification, "+" indicates a point at which the same or different atoms or chemical formulae are bonded, when a specific definition is not otherwise provided.
One embodiment provides a photosensitive resin composition comprising (A-1) a blue colorant; (a-2) a yellow dye having a maximum absorption wavelength in a wavelength region of 360 nm to 390 nm and a transmittance of 95% or more in a wavelength region of 450 nm to 900 nm; (A-3) a violet dye; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.
However, Bx of the color coordinates of a new blue color tends to become smaller recently in order to increase color reproducibility in order to realize a blue color filter having such high color reproducibility, a narrow transmission spectrum should be made in a range of 450 nm of the wavelength of a blue LED (light source), and therefore, it is suggested to manufacture a resist by using β blue pigments (e.g., c.i. pigment blue 15:3, c.i. pigment blue 15:4, etc.) instead of epsilon blue (e.g., c.i. pigment blue 15:6, etc.) which is generally used (but increasing PWC to reduce the width of the transmission spectrum).
In accordance with an embodiment, a yellow dye that reduces Bx compared to β blue but cuts off the violet region to ensure sufficient brightness is used, and the violet dye is used with the yellow dye, in order to reduce Bx (in the same By), the amount of colorant should be reduced, and in an embodiment, the total amount of colorant can be greatly reduced By using the violet dye along with the blue colorant and the yellow dye.
Hereinafter, each component is specifically described.
(A) Coloring agent
The colorant may comprise (a-1) a blue pigment, a blue dye, or a mixture thereof; (a-2) a yellow dye having a maximum absorption wavelength in a wavelength region of 360 nm to 390 nm and a transmittance of 95% or more in a wavelength region of 450 nm to 900 nm; and (a-3) a violet dye, and in one embodiment, a colorant may be included in an amount of 2 wt% to 40 wt% based on the total amount of the photosensitive resin composition.
(a-1) blue dye, blue pigment or mixture thereof
The blue dye may be represented by chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R1and R2Independently is substituted C1 to C20 alkyl or substituted or unsubstituted C3 to C20 cycloalkyl,
R3is a hydrogen atom or a halogen atom,
R4is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R5is a C1 to C20 alkyl group substituted or unsubstituted with an acrylate group, and
X-represented by one of chemical formulas a to C.
[ chemical formula A ]
SO3 -
[ chemical formula B ]
F3C-(CF2)n3-SO3
In chemical formula B, n3 is an integer in the range of 0 to 10.
[ chemical formula C ]
For example, the blue dye may be represented by chemical formula 3 or chemical formula 4. [ chemical formula 3]
[ chemical formula 4]
In chemical formula 3 and chemical formula 4,
X-represented by one of chemical formulas a to C.
[ chemical formula A ]
SO3 -
[ chemical formula B ]
F3C-(CF2)n3-SO3
In chemical formula B, n3 is an integer in the range of 0 to 10.
[ chemical formula C ]
Specifically, the blue dye may be represented by chemical formula 3.
The compound represented by chemical formula 3 includes a cyclohexyl group, and thus heat resistance may be improved. Since the phenyl group bonded to the nitrogen atom contains a methyl group, light resistance can be improved. Therefore, a color filter having durability (such as heat resistance or light resistance) and having high luminance at high color coordinates can be provided.
When blue pigments are used as blue colorants according to the examples, the use of epsilon blue pigments (rather than β blue pigments) can help to increase brightness.
For example, the blue pigment may be c.i. pigment blue 15: 6.
The blue dye or blue pigment may be a derivative bonded to an organic polymer.
The blue dye, the blue pigment, or a mixture thereof may be included in an amount of 1.5 wt% to 15 wt% (e.g., 2 wt% to 10 wt%) based on the total solid amount of the photosensitive resin composition according to the embodiment. In this range, high brightness at high color coordinates can be achieved.
(a-2) yellow dye
The yellow dye has a maximum absorption wavelength in a wavelength region of 360 nanometers to 390 nanometers and a transmittance of greater than or equal to 95% in a wavelength region of 450 nanometers to 900 nanometers.
Since Bx in CIE color coordinates should be small to achieve high color coordinates, the following method has been used: a method of red-shifting B15:3 or B15:4 from conventional B15:6 and increasing the amount thereof was used, but had a problem of great luminance degradation. Further, violet colorant has been added in accordance with the conventional sRGB content (sRGB level) to increase brightness, but here, Bx in CIE color coordinates becomes larger, and high color coordinates may not be achievable. However, according to the embodiment, a yellow colorant (and specifically, a yellow dye) is used instead of B15:3 and B15:4, and the yellow dye is adjusted to have transmittance according to the wavelength as described above, and thus the loss of brightness can be minimized. Further, yellow dyes block wavelengths ranging from 360 to 390 nanometers (i.e., short wavelength regions), and herein, yellow dyes may also have a vision-protecting effect, as short wavelengths typically irritate the eye and degrade vision.
The yellow dye may be an azo-type dye.
The yellow dye may be included in an amount of 0.01 wt% to 1 wt% (e.g., 0.05 wt% to 0.5 wt%) based on the total amount of the photosensitive resin composition according to the embodiment. When a yellow dye is included in the range, high brightness in high color coordinates can be achieved, and the eye protection effect can be maximized. Herein, the yellow dye may be included in a smaller amount than the amount of the violet dye. When the yellow dye is contained in an amount of the violet dye or more, there is a problem that luminance is deteriorated and a process margin (process margin) is insufficient.
(A-3) purple dye
The violet dye may be represented by chemical formula 1-1 or chemical formula 1-2.
[ chemical formula 1-1]
[ chemical formulas 1-2]
In chemical formula 1-1 and chemical formula 1-2,
R101to R105Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R106is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,
R107is a substituted or unsubstituted C3 to C20 cycloaliphatic ring radicalOr a substituted or unsubstituted C6 to C20 aryl group,
R108to R110Independently a substituted or unsubstituted C1 to C20 alkyl group,
n is an integer in the range of 1 to 5, and
l is represented by chemical formula 1-3,
[ chemical formulas 1-3]
*-L1-A
Wherein, in chemical formulas 1 to 3,
L1is-O (C ═ O) -,
a is a substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 alicyclic ring group, or substituted or unsubstituted C6 to C20 aryl group.
In chemical formula 1-2, L may be represented by one of chemical formulas 1-3-1 to 1-3-5.
[ chemical formula 1-3-1]
[ chemical formulas 1-3-2]
[ chemical formulas 1-3-3]
[ chemical formulas 1-3-4]
[ chemical formulas 1-3-5]
In chemical formulas 1-3-1 to 1-3-5,
R111is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group,
R112to R114Independently is hydroxy or substituted or unsubstituted C1 to C10 alkyl with the proviso that R is112And R113At least one of which is a hydroxyl group,
R115is a substituted or unsubstituted C1 to C10 alkyl group,
o and p are independently integers in the range of 1 to 3 with the proviso that 2. ltoreq. o + p. ltoreq.5, and
q is an integer in the range of 0 to 4.
For example, in the violet dye represented by chemical formula 1-2, R106May be a hydrogen atom, R107May be substituted or unsubstituted adamantyl, R108To R110May be independently a substituted or unsubstituted C1 to C20 alkyl group, and L may be represented by chemical formula 1-3-1.
The violet dye represented by chemical formula 1-1 is effective in significantly reducing the amount of the above blue colorant and yellow dye. The violet dye represented by chemical formula 1-2 can slightly reduce the amount of blue colorant and yellow dye used, but it can effectively increase brightness even at high color coordinates.
The violet dye may be included in an amount of 0.1 to 2 wt% (e.g., 0.2 to 1 wt%) based on the total amount of the photosensitive resin composition according to the embodiment. When the violet dye is included in the above range, the amounts of the above blue dye, blue pigment or a mixture thereof, and yellow pigment may be reduced, so that a color coordinate (e.g., CIE color coordinate) having a Bx value less than or equal to 0.148 at a By value of 0.0510 which is at a high color coordinate may be realized, and high luminance may be realized in the high color coordinate.
(B) Adhesive resin
The binder resin may comprise an acryl-based binder resin, a cardo-based binder resin, or a combination thereof.
The acryl-based binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one acryl-based repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer comprising at least one carboxyl group, and examples of the monomer comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or combinations thereof.
The first ethylenically unsaturated monomer may be included in an amount of 5 to 50 wt% (e.g., 10 to 40 wt%), based on the total amount of the acryl based binder resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene, α -methylstyrene, vinyltoluene, vinylbenzyl methyl ether and the like, an unsaturated carboxylic acid ester compound such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and the like, an unsaturated carboxylic acid aminoalkyl ester compound such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate and the like, a carboxylic acid vinyl ester compound such as vinyl acetate, vinyl benzoate and the like, an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth) acrylate and the like, a vinyl cyanide compound such as (meth) acrylonitrile and the like, an unsaturated amide compound such as (meth) acrylamide and the like, and may be used alone or in a mixture of two or more.
Specific examples of the acryl-based binder resin may be (meth) acrylic acid/benzyl methacrylate copolymer, (meth) acrylic acid/benzyl methacrylate/styrene copolymer, (meth) acrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth) acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in a mixture of two or more.
The weight average molecular weight of the acryl based binder resin may be 3,000 g/mole to 150,000 g/mole, for example, 5,000 g/mole to 50,000 g/mole, for example, 20,000 g/mole to 30,000 g/mole. When the acryl based binder resin has a weight average molecular weight within the range, the photosensitive resin composition may have excellent physical and chemical characteristics and appropriate viscosity, maintain appropriate developability and sensitivity, and exhibit excellent close contact characteristics with a substrate during color filter manufacturing.
The acid value of the acryl based binder resin may be 15 mgKOH/g to 60 mgKOH/g, for example, 20 mgKOH/g to 50 mgKOH/g. When the acryl based binder resin has an acid value within the range, excellent pixel resolution can be obtained.
The cardo-based binder resin may be represented by chemical formula 10.
[ chemical formula 10]
In the chemical formula 10, the first and second,
R101and R102Independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,
R103and R104Independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
Z1is a single bond, O, CO, SO2、CR107R108、SiR109R110(wherein, R107To R110Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group) or a linking group represented by chemical formula 10-1 to chemical formula 10-11,
[ chemical formula 10-1]
[ chemical formula 10-2]
[ chemical formula 10-3]
[ chemical formula 10-4]
[ chemical formula 10-5]
In the chemical formula 10-5,
Rzis a hydrogen atom, an ethyl group, C2H4Cl、C2H4OH、CH2CH＝CH2Or a phenyl group.
[ chemical formula 10-6]
[ chemical formulae 10-7]
[ chemical formulae 10-8]
[ chemical formulae 10-9]
[ chemical formulae 10 to 10]
[ chemical formulae 10 to 11]
Z2Is an acid anhydride moiety or an acid dianhydride moiety, and
z1 and z2 are independently integers in the range of 0 to 4.
The weight average molecular weight of the pyridoxine-based binder resin may be from 500 g/mole to 50,000 g/mole, such as from 1,000 g/mole to 30,000 g/mole. When the weight average molecular weight of the pyridox-based binder resin is within the range, a satisfactory pattern can be formed without residue during the manufacture of the light-blocking layer and without loss of film thickness during development.
The pyridoxine-based binder resin may include a functional group represented by chemical formula 11 at least one of the two terminals.
[ chemical formula 11]
In the chemical formula 11, the first and second,
Z3represented by chemical formula 11-1 to chemical formula 11-7.
[ chemical formula 11-1]
In chemical formula 11-1, RhAnd RiIndependently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, an ester group, or an ether group.
[ chemical formula 11-2]
[ chemical formula 11-3]
[ chemical formulas 11-4]
[ chemical formulas 11-5]
In chemical formula 11-5, RjIs O, S, NH, a substituted or unsubstituted C1 to C20 alkylene group, a C1 to C20 alkylamino group, or a C2 to C20 alkenylamino group.
[ chemical formulas 11-6]
[ chemical formulae 11-7]
The pyridoxine-based binder resin may be prepared, for example, by mixing at least two of the following: fluorene-containing compounds such as 9, 9-bis (4-oxiranylmethoxyphenyl) fluorene; anhydride compounds such as benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, perylenetetracarboxylic dianhydride, tetrahydrofurantetracarboxylic dianhydride, and tetrahydrophthalic anhydride (tetrahydrophthalic anhydride); glycol compounds such as ethylene glycol, propylene glycol, and polyethylene glycol; alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol, and benzyl alcohol; solvent-based compounds such as propylene glycol methyl ethyl acetate and N-methyl pyrrolidone; phosphorus compounds such as triphenylphosphine; and amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, or benzyltriethylammonium chloride.
When the binder resin comprises a cardo-type binder resin, the photosensitive resin composition has excellent developability and sensitivity during photocuring and thus fine patternability.
The binder resin may be included in an amount of 3 to 20 wt% (e.g., 5 to 15 wt%), based on the total amount of the photosensitive resin composition. When the binder resin is included within the range, since crosslinking is improved during the manufacture of the color filter, developability may be improved and surface smoothness may be improved.
(C) Photopolymerizable compounds
The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid containing at least one ethylenically unsaturated double bond.
The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization during exposure in a pattern-forming process and form a pattern having excellent heat resistance, light resistance, and chemical resistance.
Specific examples of the photopolymerizable compound may be ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol a di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol a epoxy (meth) acrylate, and the like, Ethylene glycol monomethyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate, and the like.
Examples of commercially available photopolymerizable compounds are as follows. The monofunctional (meth) acrylate may comprise anix (Aronix)
(Toagosei chemical industry Co., Ltd.); kayarad (KAYARAD)
(Nippon Kayaku Co., Ltd.,. Ltd.);
(Osaka organic Chemical industry, Ltd.) and the like. Examples of difunctional (meth) acrylates may include anixox
(Toyo Synthesis chemical industry Co., Ltd.); ka ya Red
(Nippon Kagaku Co., Ltd.);
(Osaka organic chemical industries Co., Ltd.) and the like. Examples of trifunctional (meth) acrylates may include anixox
(Toyo Synthesis chemical industry Co., Ltd.); ka ya Red
(Nippon Kagaku Co., Ltd.);
(Osaka, Shibata, Kyoki Kayaku Kogyo Co., Ltd.) and the like. These may be used alone or in a mixture of two or more.
The photopolymerizable compound may be anhydride treated to improve developability.
The photopolymerizable compound may be included in an amount of 1 to 10 wt% (e.g., 3 to 8 wt%), based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the range, the photopolymerizable monomer is sufficiently cured during exposure in the pattern forming process and has excellent reliability, and the developability of the alkaline developer can be improved.
(D) Photopolymerization initiator
The photopolymerization initiator may be an initiator commonly used in photosensitive resin compositions, such as acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, oxime compounds, or a combination thereof.
Examples of the acetophenone compounds may be 2,2' -diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like.
Examples of the benzophenone-based compound may be benzophenone, benzoylbenzoate, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4' -bis (dimethylamino) benzophenone, 4' -bis (diethylamino) benzophenone, 4' -dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3' -dimethyl-2-methoxybenzophenone and the like.
Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.
Examples of benzoin-based compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.
Examples of triazines are 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) s-triazine (2-phenyl-4, 6-bis (trichloromethyl) -s-triazine), 2- (3',4' -dimethoxystyryl) -4,6-bis (trichloromethyl) s-triazine (2- (3',4' -dimethylosytyryl) -4,6-bis (trichloromethyl) -s-triazine), 2- (4' -methoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine (2- (4' -methoxyxyphenyl) -4,6-bis (trichloromethyl) -s-triazine), 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) s-triazine (2- (4' -methoxyxyphenyl) -4,6-bis (trichloromethyl) -s-triazine), 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) s-triazine (2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine), 2-biphenyl 4,6-bis (trichloromethyl) s-triazine (2-biphenol 4,6-bis (trichloromethyl) -s-triazine), bis (trichloromethyl) -6-styryl s-triazine (bis (trichloromethyl) -6-styryl-s-triazine), 2- (naphthol) -4,6-bis (trichloromethyl) s-triazine (2- (naphtho1-yl) -4,6-bis (trichloromethyl) s-triazine), 2- (4-methoxynaphthol) -4,6-bis (trichloromethyl) s-triazine (2- (4-methoxylphtho 1-yl) -4,6-bis (trichloromethyl) -s-triazine), 2-4-bis (trichloromethyl) -6-sunflower-based s-triazine (2-4-bis (trichloromethyl) -6-piperonyl-s-triazine), 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) s-triazine (2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine) and the like.
Examples of the oxime compound may be an O-acyloxime compound (O-acyloxime-based compound), 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione (2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl ] -1, 2-octanedione), 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone (1- (O-acetyloxime) -1- [9-ethyl-6- (2-phenylthio) -9H-carbazol-3-yl ] ethanone), O-ethoxycarbonyl- α -oxyamino-1-phenylpropan-1-one (O-ethoxycarbonyl- α -oxoamino-1-phenylpropan-1-one (O-phenyloxime-1-oxoethyl-6- (2-phenylthio) -1-phenyl-1-one), and specific examples thereof may be an O-acyloxime compound (O-phenyloxime) -1- [4- (phenylthio) -phenyl ] -1, 2-oxobutyl-4- (2-phenylthiobutyl) -1-2-oxoethyl-1-3-yl ] ethanone, and analogs thereof (O-acetyloxime-1- (2-phenyl) -1-2-phenyl-oxobutyl-4- (2-phenyl) -4-phenyl-oxoketone), and examples of the compound may be an-2-oxobutyl-4-2-oxoketone-phenyl-4- (2-phenyl) -1-oxobutyl-phenyl-4-phenyl-4-oxoketone-1-4-oxoketone, 4-phenyl-oxomethyl-phenyl-methyl-4-methyl-phenyl-1-methyl-4-phenyl-4-methyl-4-ethyl-phenyl-1-phenyl-ethyl-4-methyl-1-ethyl-methyl-ethyl-4-ethyl-phenyl-4-ethyl-methyl-1-ethyl-4-methyl-1-ethyl-phenyl-methyl-ethyl-methyl-1-ethyl-ketone-1-4-ethyl-4-ethyl-phenyl-methyl-phenyl-ethyl-1-methyl-phenyl-ethyl-1-phenyl-ethyl-phenyl-1-4-phenyl-ethyl-4-phenyl-ethyl-1-ethyl-1-4-methyl-phenyl-ethyl-ketone-4-ethyl-ketone-methyl-4-methyl-ethyl-phenyl-ketone-.
The photopolymerization initiator may further include, in addition to the compounds, carbazole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazonium-based compounds, imidazole-based compounds, bisimidazole-based compounds, fluorene-based compounds, and the like.
The photopolymerization initiator may be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming an excited state and then transferring its energy.
Examples of the sensitizer may be tetraethylene glycol bis-3-mercaptopropionate (tetraethylene glycol bis-3-mercapto propionate), pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.
The photopolymerization initiator may be included in an amount of 0.1 to 5 wt% (e.g., 0.1 to 3 wt%) based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the range, sufficient photopolymerization occurs during exposure in the pattern forming process, excellent reliability can be achieved, heat resistance, light resistance, and chemical resistance, resolution, and close contact characteristics of the pattern can be improved, and transmittance can be prevented from being reduced due to the non-reactive initiator.
(E) Solvent(s)
The solvent is a material having compatibility with, but not reacting with, the colorant, the binder resin, the photopolymerizable compound, and the photopolymerization initiator.
Examples of the solvent may include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and the like; ethylene glycol acetates (cellosolve acetates), such as methyl ethylene glycol acetate, ethyl ethylene glycol acetate, diethyl ethylene glycol acetate, and the like; carbitols (carbitols) such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene, and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl n-acetone, methyl n-butanone, methyl n-pentanone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactates such as methyl lactate, ethyl lactate, and the like; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, and the like; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like; alkyl 3-oxopropionates such as methyl 3-oxopropionate, ethyl 3-oxopropionate, and the like; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and the like; alkyl 2-oxopropanates such as methyl 2-oxopropanate, ethyl 2-oxopropanate, propyl 2-oxopropanate and the like; alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, and the like; 2-oxo-2-methylpropionates such as methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate and the like; mono-oxo-monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionates, such as methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, and the like; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate, 2-hydroxy-3-methyl butyrate, and the like; ketoesters such as ethyl pyruvate and the like. In addition, high boiling point solvents such as N-methylformamide, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone (isophorone), hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ -butyrolactone, ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), ethylene glycol ethyl ether phenyl acetate, and the like may also be used.
In view of mutual solubility and reactivity, ketones such as cyclohexanone and the like; ethylene glycol alkyl ether acetates such as ethyl ethylene glycol ethyl acetate and the like; esters such as 2-hydroxyethyl propionate and the like; carbitols such as diethylene glycol monomethyl ether and the like; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate.
The solvent is used in a balance (e.g., 25 to 80 wt%) based on the total amount of the photosensitive resin composition. When the solvent is included within the range, the photosensitive resin composition may have an appropriate viscosity, thereby improving the coating characteristics of the color filter.
(F) Other additives
The photosensitive resin composition according to another embodiment may further include an epoxy compound to improve the close contact property with the substrate.
Examples of the epoxy compound may include phenol novolac epoxy compounds (phenonol novolac epoxy compounds), tetramethyl biphenyl epoxy compounds, bisphenol a epoxy compounds, alicyclic epoxy compounds, or combinations thereof.
The epoxy compound may be included in an amount of 0.01 parts by weight to 20 parts by weight (e.g., 0.1 parts by weight to 10 parts by weight) based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained within the range, the close contact property, the storage property, and the like can be improved.
In addition, the photosensitive resin composition may further include a silane coupling agent having a reactive substituent (such as a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and the like) in order to improve its adhesion to a substrate.
Examples of the silane-based coupling agent may include trimethoxysilylbenzoic acid, gamma-methylpropenyl (gamma-methacryl) propoxytrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanate (gamma-isocyanate) propyltriethoxysilane, gamma-glycidoxy (gamma-glycidoxy) propyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (β -3,4(epoxycyclohexyl) ethyltrimethoxysilane), and the like.
The silane coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within the range, the close contact property, the storage property, and the like may be excellent.
In addition, if necessary, the photosensitive resin composition may further include a surfactant to improve coating characteristics and prevent defects.
Examples of the surfactant may be commercially available fluorine-based surfactants such as those of BM Chemieinc
And the like; megaffei (MEGAFACE) of Dainippon ink chemical industry Co., Ltd (Dainippon ink Kagaku Kogyo Co., Ltd.)
And the like; fohlera (FULORAD) of Sumitomo Business 3M corporation (Sumitomo 3MCo., Ltd.)
And the like; surflon (SURFLON) of Asahi Glass company (ASAHI Glass Co., Ltd.)
And the like;
and the like.
The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the surfactant is contained within the range, coating uniformity is ensured, no staining is found, and the wetting property of the glass substrate is excellent.
Further, unless the characteristics deteriorate, the photosensitive resin composition may further contain other additives such as an oxidation inhibitor, a stabilizer, and the like in a predetermined amount.
According to another embodiment, there is provided a photosensitive resin layer manufactured using the photosensitive resin composition according to the embodiment.
The pattern formation process in the photosensitive resin layer is as follows.
The process comprises the following steps: coating the photosensitive resin composition according to the embodiment on a support substrate by spin coating, slit coating, inkjet printing, and the like; drying the coated positive photosensitive resin composition to form a photosensitive resin composition layer; exposing the positive photosensitive resin composition layer to light; developing the exposed positive photosensitive resin composition layer in an alkaline aqueous solution to obtain a photosensitive resin layer; and performing heat treatment on the photosensitive resin layer. The conditions of the patterning process are well known in the art and will not be described in detail in the specification.
According to an embodiment, a color filter including a photosensitive resin layer is provided.
Hereinafter, the present invention is described in more detail with reference to examples, which, however, are not to be construed in any way as limiting the scope of the present invention.
(Synthesis of yellow dye)
Synthesis example 1 Synthesis of yellow dye
To 4-aminophthalitrile (4-aminophthalitrile) (2.5 mmol)) were added hydrochloric acid (2.5 ml) and sodium nitrate (2 ml of a 1.25 molar aqueous solution), and the azo (azonium) ion obtained therefrom was placed in a weakly alkaline aqueous solution prepared by dissolving barbituric acid (2.5 mmol) in an aqueous NaOH solution to obtain an azo compound. Herein, the solid obtained therefrom was filtered, purified and vacuum-dried, followed by reacting the solid with 1-iodobutane (5.5 mmol) and potassium carbonate (7.5 mmol) in a DMF solvent, and then, purified and vacuum-dried to obtain yellow dye 1.
(Synthesis of purple dye)
Synthesis example 2
(1) Synthesis of Compound represented by the formula A
To DMF (dimethylformamide, 250 ml) was added 2-bromoacetophenone (1 mol), and then stirred at room temperature. To the reaction solution was added potassium phthalimide (0.95 mol), and the resulting mixture was stirred for 3 hours. When the reaction was completed, precipitation was performed using 2500 ml of water, and the resulting precipitate was filtered and dried to obtain the compound represented by chemical formula a (yield: 78%).
(2) Synthesis of Compound represented by the formula B
To 500 ml of toluene were added cyanoacetic acid (1.46 mol) and 2, 6-di-t-butyl-4-methylcyclohexanol (1.33 mol), and then stirring was performed at room temperature. Pyridine (1.59 mol) was added to the reaction solution, and then stirring was performed. To this solution was added anhydrous acetic acid (2.65 mol), and then it was stirred for 6 hours to complete the reaction. The reaction solution was washed twice with 500 g of a 10% aqueous hydrochloric acid solution, and then twice with 500 g of an aqueous sodium chloride solution. Water was removed therefrom using magnesium sulfate, and the resulting product was filtered and dried to obtain a compound represented by chemical formula B (yield: 62.5%).
(3) Synthesis of Compound represented by formula C
To a mixed solution of 10 ml of methanol and 10 ml of water, a compound represented by formula a (3.8 mol) and a compound represented by formula B (4.15 mol) were added, and then stirred. A 48% aqueous sodium hydroxide solution (8.36 moles) was added to the reaction solution in a dropwise manner, and then the solution was heated to 70 ℃ and stirred for 3 hours. After monitoring the reaction by TLC, the reaction was complete. The resultant was cooled to room temperature, filtered and then washed with water and hexane, and dried to obtain the compound represented by chemical formula C (yield: 69%).
(4) Synthesis of Compound represented by formula D
To 800 g of acetic acid was added the compound represented by the formula C (0.38 mol), and then stirred at room temperature. To this solution was added triethyl orthoformate (0.23 mol), and then it was heated and stirred for 10 hours. When the reaction was completed, the resultant was filtered with 100 g of acetonitrile, and 100 g of acetonitrile was added thereto, and then stirring was performed. This solution was filtered, washed with 100 g of acetonitrile, and dried to obtain a compound represented by formula D (yield: 68.7%).
(5) Synthesis of Compound represented by formula E
The compound represented by formula D was added to 17 ml of toluene, and then stirred. To this solution (40% aqueous solution, 0.036 mmol) was added sodium hydroxide in a dropwise manner. Subsequently, TBAB (tetrabutylammonium bromide), 0.0012 mmol, was added thereto at room temperature, and then stirred for 30 minutes and cooled to 0 ℃ by using an ice bath. To the reaction solution was added 1-adamantane (adamantane) acid chloride (0.072 mmol). After removing the ice bath and then stirring the resulting mixture for 2 hours, the reaction was complete upon raising the temperature to room temperature. The resultant was washed with 100 ml of water and 100 ml of ethyl acetate and dried to obtain the compound represented by the formula E (yield: 72.5%).
(6) Synthesis of Compound represented by formula F
To a mixed solution of 60 ml of water/90 ml of methanol, 4-tributyl benzoate (0.14 mol) and sodium methoxide (30% methanol solution, 0.14 mol) were added, and then stirring was performed. To this solution was added zinc sulfate 7 hydrate (0.06 mol). The resulting mixture was stirred at room temperature for 1 hour to complete the reaction. After the reaction, the resultant was washed with 1000 ml of water and 1000 ml of methanol to obtain the compound represented by the formula F (yield: 90.1%).
(7) Synthesis of Compound represented by the formula G
To 10 ml of ethanol were added the compound represented by formula E (0.642 mmol) and the compound represented by formula F (0.835 mmol), and then stirring was performed at room temperature. TCL was used to verify the reaction, and then the reaction was complete. After drying the ethanol of the reaction solution, the product obtained therefrom was washed with 100 ml of dichloromethane and 100 ml of water to obtain a compound (dye) represented by chemical formula G. (yield: 81.7%, matrix assisted laser desorption ionization time-of-flight Mass spectrometry (Maldi tof Mass): 1454.8)
(Synthesis of photosensitive resin composition)
Examples 1 and 2 and comparative examples 1 to 4
The following components were mixed in the compositions shown in table 1 to prepare photosensitive resin compositions according to example 1, example 2, and comparative examples 1 to 4.
Specifically, a photopolymerization initiator is dissolved in a solvent, the solution is stirred at room temperature for 2 hours, a binder resin and a photopolymerizable compound are added thereto, and the resulting mixture is stirred at room temperature for 2 hours. Subsequently, a blue pigment dispersion, a yellow dye, and a violet dye as a colorant and other additives were added to the reaction mixture, and the resulting mixture was stirred at room temperature for 1 hour. Subsequently, the product obtained therefrom was filtered three times to remove impurities, thereby preparing each photosensitive resin composition.
[ Table 1]
(unit: wt%)
(A) Coloring agent
(a-1) C.I. pigment blue 15:6 Dispersion (Sanyo (SANYO); pigment solids content 10%)
(a-2) yellow dye: synthesis of the Compound of example 1
(a-3) purple dyes
(a-3-1) purple 2B (Kyung-In Synthetic Corporation, Korea)
(a-3-2) Synthesis of the Compound of example 2 (Compound represented by formula G)
(B) Adhesive resin
Acryl based adhesive resin (SP-RY-25, Showa Denko)
(C) Photopolymerizable compounds
Dipentaerythritol hexaacrylate (DPHA) (Nippon Kabushiki Kaisha)
(D) Photopolymerization initiator
OXE01 (Basf)
(E) Solvent(s)
PGMEA (Kyowa co., Ltd.)
(F) Additive agent
Fluorine-based surfactant (F-554, Dai Nippon ink chemical Co., Ltd. (DIC Co., Ltd.))
Evaluation: color coordinates and brightness
Each of the photosensitive resin compositions of example 1, example 2, and comparative examples 1 to 4 was coated to a thickness of 1 to 3 micrometers at 250 to 350 revolutions per minute on a 1 mm thick degreased and washed glass substrate, and then dried on a heating plate at 90 ℃ for 2 minutes to obtain a film. Subsequently, the film was exposed to light at 50 mj/cm by using a main wavelength high-pressure mercury lamp having 365 nm, and the film was developed for 60 seconds by using a KOH developing solution (111 times diluted solution) under the condition of 1/0.8 of a washing liquid/developing solution and additionally washed for 60 seconds. Subsequently, the film was dried in a forced convection drying oven at 230 ℃ for 20 minutes to obtain each color specimen (color chart).
The color characteristics of the color specimen of the reference C light source were evaluated By using a spectrophotometer (MCPD3000, tsukamur Electronics co., Ltd.), the luminance Y was calculated based on the CIE color coordinates (By 0.0510), and the results are shown in table 2.
[ Table 2]
Referring to table 2, when a blue colorant, a yellow dye having a maximum absorption wavelength in a wavelength region of 360 to 390 nm and a transmittance of greater than or equal to 95% in a wavelength region of 450 to 900 nm, and a violet dye are simultaneously used, a high color coordinate is achieved, and simultaneously excellent luminance is achieved. Specifically, when the blue colorant, the yellow colorant, and the violet colorant are simultaneously used according to examples 1 and 2 and comparative example 1, high color coordinates are achieved, and at the same time, luminance degradation is prevented by reducing the total amount of the colorant. Further, comparative examples 2 to 4, which did not have the colorant composition according to the examples, showed excellent luminance, but did not achieve high color coordinates.
While the invention has been described in connection with what is presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (14)
1. A photosensitive resin composition comprising:
(A) a colorant comprising the following (a-1) to (a-3):
(a-1) a blue pigment, a blue dye, or a mixture thereof;
(a-2) a yellow dye having a maximum absorption wavelength in a wavelength region of 360 nm to 390 nm and a transmittance of 95% or more in a wavelength region of 450 nm to 900 nm, and
(a-3) a violet dye;
(B) a binder resin;
(C) a photopolymerizable compound;
(D) a photopolymerization initiator; and
(E) a solvent.
2. The photosensitive resin composition according to claim 1, wherein the violet dye is contained in an amount of 0.1 to 2% by weight based on the total amount of the photosensitive resin composition.
3. The photosensitive resin composition according to claim 1, wherein the violet dye is represented by chemical formula 1-1 or chemical formula 1-2:
[ chemical formula 1-1]
[ chemical formulas 1-2]
Wherein, in chemical formula 1-1 and chemical formula 1-2,
R101to R105Independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, or a substituted or unsubstituted C6 to C20 aryl group,
R106is a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkoxy group or a substituted or unsubstituted C6 to C20 aryl group,
R107is a substituted or unsubstituted C3 to C20 cycloaliphatic ring radical or a substituted or unsubstituted C6 to C20 aryl radical,
R108to R110Independently a substituted or unsubstituted C1 to C20 alkyl group,
n is an integer in the range of 1 to 5, and
l is represented by chemical formula 1-3,
[ chemical formulas 1-3]
*-L1-A
Wherein, in chemical formulas 1 to 3,
L1is-O (C ═ O) -, and
a is a substituted or unsubstituted C1 to C20 alkyl, substituted or unsubstituted C3 to C20 alicyclic ring group, or substituted or unsubstituted C6 to C20 aryl group.
4. The photosensitive resin composition according to claim 3, wherein L is represented by one of chemical formulae 1-3-1 to 1-3-5:
[ chemical formula 1-3-1]
[ chemical formulas 1-3-2]
[ chemical formulas 1-3-3]
[ chemical formulas 1-3-4]
[ chemical formulas 1-3-5]
Wherein, in chemical formulas 1-3-1 to 1-3-5,
R111is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted amino group, or a substituted or unsubstituted acyl group,
R112to R114Independently is hydroxy or substituted or unsubstituted C1 to C10 alkyl with the proviso that R is112And R113At least one of which is a hydroxyl group,
R115is a substituted or unsubstituted C1 to C10 alkyl group,
o and p are independently integers in the range of 1 to 3 with the proviso that 2. ltoreq. o + p. ltoreq.5, and
q is an integer in the range of 0 to 4.
5. The photosensitive resin composition according to claim 4, wherein in the violet dye represented by chemical formula 1-2,
R106is hydrogenThe number of atoms,
R107is a substituted or unsubstituted adamantyl group,
R108to R110Independently a substituted or unsubstituted C1 to C20 alkyl group, and
l is represented by chemical formula 1-3-1.
6. The photosensitive resin composition according to claim 1, wherein
The yellow dye is an azo dye.
7. The photosensitive resin composition according to claim 1, wherein the yellow dye is contained in an amount of 0.01 to 1% by weight based on the total amount of the photosensitive resin composition.
8. The photosensitive resin composition of claim 1, wherein the yellow dye is included in a smaller amount than the violet dye, and the violet dye is included in a smaller amount than the blue pigment, blue dye, or a mixture thereof.
9. The photosensitive resin composition according to claim 1, wherein the binder resin comprises an acryl-based binder resin, a cardo-based binder resin, or a combination thereof.
10. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises, based on the total amount of the photosensitive resin composition
2 to 40 weight percent of the colorant;
3 to 20 weight percent of the binder resin;
1 to 10% by weight of the photopolymerizable compound;
0.1 to 5% by weight of the photopolymerization initiator, and
the balance of the solvent.
11. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.
12. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a Bx value of less than or equal to 0.148 when the By value is 0.0510 in CIE color coordinates.
13. A photosensitive resin layer produced using the photosensitive resin composition according to any one of claims 1 to 12.
14. A color filter comprising the photosensitive resin layer according to claim 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020180103735A KR102338286B1 (en) | 2018-08-31 | 2018-08-31 | Photosensitive resin composition, photosensitive resin using the same and color filter |
| KR10-2018-0103735 | 2018-08-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110874013A true CN110874013A (en) | 2020-03-10 |
Family
ID=69717086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910400724.8A Pending CN110874013A (en) | 2018-08-31 | 2019-05-15 | Photosensitive resin composition, photosensitive resin layer using same, and color filter |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR102338286B1 (en) |
| CN (1) | CN110874013A (en) |
| TW (1) | TWI705300B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184568A1 (en) * | 2022-03-30 | 2023-10-05 | 苏州华星光电技术有限公司 | Photoresist and display device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013113973A (en) * | 2011-11-28 | 2013-06-10 | Toppan Printing Co Ltd | Color filter for liquid crystal display device, and liquid crystal display device |
| CN106597808A (en) * | 2015-10-14 | 2017-04-26 | 三星Sdi株式会社 | Photosensitive resin composition, photosensitive resin film using the same and color filter |
| KR20170088631A (en) * | 2016-01-25 | 2017-08-02 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer and color filter comprising the same |
| CN107129482A (en) * | 2016-02-26 | 2017-09-05 | 三星Sdi株式会社 | Compounds, novel polymeric, the colouring agent comprising it, positive type photosensitive organic compound and colour filter comprising it |
| CN107540697A (en) * | 2016-06-24 | 2018-01-05 | 三星Sdi株式会社 | Compound, the photosensitive polymer combination and colored filter for including it |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101804259B1 (en) * | 2015-03-24 | 2017-12-04 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black column spacerusing the same and color filter |
| KR102061245B1 (en) * | 2016-12-05 | 2019-12-31 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
-
2018
- 2018-08-31 KR KR1020180103735A patent/KR102338286B1/en active IP Right Grant
-
2019
- 2019-05-03 TW TW108115309A patent/TWI705300B/en active
- 2019-05-15 CN CN201910400724.8A patent/CN110874013A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013113973A (en) * | 2011-11-28 | 2013-06-10 | Toppan Printing Co Ltd | Color filter for liquid crystal display device, and liquid crystal display device |
| CN106597808A (en) * | 2015-10-14 | 2017-04-26 | 三星Sdi株式会社 | Photosensitive resin composition, photosensitive resin film using the same and color filter |
| KR20170088631A (en) * | 2016-01-25 | 2017-08-02 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer and color filter comprising the same |
| CN107129482A (en) * | 2016-02-26 | 2017-09-05 | 三星Sdi株式会社 | Compounds, novel polymeric, the colouring agent comprising it, positive type photosensitive organic compound and colour filter comprising it |
| CN107540697A (en) * | 2016-06-24 | 2018-01-05 | 三星Sdi株式会社 | Compound, the photosensitive polymer combination and colored filter for including it |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023184568A1 (en) * | 2022-03-30 | 2023-10-05 | 苏州华星光电技术有限公司 | Photoresist and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102338286B1 (en) | 2021-12-09 |
| TW202011118A (en) | 2020-03-16 |
| TWI705300B (en) | 2020-09-21 |
| KR20200025819A (en) | 2020-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107621753B (en) | Photosensitive resin composition, photosensitive resin layer using same, and display device | |
| CN104950600B (en) | Method of manufacturing black column spacer, black column spacer and color filter | |
| CN108445713B (en) | Photosensitive resin composition, black pixel defining layer using same, and display device | |
| CN106019826B (en) | Photosensitive resin composition, black column spacer using same, and color filter | |
| CN106980234B (en) | Photosensitive resin composition, photosensitive resin layer containing same and color filter | |
| CN105093831B (en) | Photosensitive resin composition and color filter using same | |
| CN108957951B (en) | Photosensitive resin composition, photosensitive resin layer using same, and color filter | |
| CN110244511B (en) | Photosensitive resin composition and layer thereof, adhesive composition and adhesive film thereof, color filter, polarizing plate and optical display device | |
| CN111221216B (en) | Photosensitive resin composition, photosensitive resin layer, and color filter layer | |
| CN107805237B (en) | Compound, photosensitive resin composition containing same, and color filter | |
| CN107129482B (en) | Novel compound, novel polymer, colorant comprising the same, positive photosensitive resin composition comprising the same, and color filter | |
| CN107522704B (en) | Novel compound, photosensitive resin composition containing same and color filter | |
| KR102023158B1 (en) | Photosensitive resin composition, photosensitive resin layer using the same and color filter | |
| CN108003593B (en) | Photosensitive resin composition, black photosensitive resin layer, and color filter | |
| CN108445712B (en) | Photosensitive resin composition, black pixel defining layer using same, and display device | |
| KR102124126B1 (en) | Novel compound, photosensitive resin composition including the same and color filter | |
| CN110874013A (en) | Photosensitive resin composition, photosensitive resin layer using same, and color filter | |
| CN112391063B (en) | Dye compound, photosensitive resin composition, photosensitive resin layer, color filter, and display device | |
| CN107540697B (en) | Compound, photosensitive resin composition containing same, and color filter | |
| CN107129481B (en) | Novel compound, colorant comprising the same, positive photosensitive resin composition comprising the colorant, and color filter | |
| CN108132583B (en) | Photosensitive resin composition, black pixel defining layer using same, and display device | |
| CN108475018B (en) | Photosensitive resin composition, black columnar spacer using same, and color filter | |
| CN113946102B (en) | Photosensitive resin composition, photosensitive resin film using same, and color filter | |
| CN112745326B (en) | Phthalocyanine compound, photosensitive resin composition, photosensitive resin layer, color filter and display device | |
| KR102624673B1 (en) | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |